5

WATER CHEMISTRY

5.1 INTRODUCTION
Water is surcly God's grecatest gift to mankind. The very existence of life cannot be
imagined without water. One can live without food, shelter or any other thing but life without
watcr is just not possible. Even our body contains around 70% water in it. From an engineer's
point of view. water is no less important. It is roquired in boilers for production of steam, which
acts as a source of energy, as a coolant in many power and chemical plants, in steel, paper,
textile, ice and many other such industrics. Despite its incredible importance, water is receiving
least attention and is getting contaminated in ways beyond description.
Water (H,0) is a polar inorganic compound which is a tasteless, odorless liquid and
colorless compound at room temperature. It is by far the most studied chemical compound and
Is described as the universal solvent. It is the most abundant substance on earth and the only
common substance to exist as a solid, liquid, and gas on earth's surface. It is also the third most
abundant molecule in the universe.

Water molecules form hydrogen bonds with each other and are strongly polar. Its
hydrogen bonding imparts its many unique properties, such as having a solid form less dense
than its liquid form, a relatively high boiling point of 100°C for its molar mass, and a high heat
capacity.
The chemistry of water is based upon its unique physical and chemical properties and
due to its unique properties, water has
acquired special status as a compound. Although there
are no limits to discuss water chemistry, but we will discuss the water
the
chemistry bricfly
under
following important subtitles in this
chapter
() Composition of water
()Structure, bonding and shape of water molecule
(11) Physical properties
(iv) Hardness of water

(233)
234
CONCEPTUAL ENGINEERING C
(v) Polarity and hydrogcn bonding of water and ico NEM13TRY
(vi) Density of water is maximum at 4 degree Celsius

(vii) Autoionization of water

(vii) Levelling effect of watcr and acid base character
Gix) Amphiprotic nature
(x) Chemical propertics of water
(xi) Water as a solvent
5.2 COMPOSITION OF WATER
Water contains onlyhydrogen and oxygen. Both the clements have natural eth
radioactive isotopes. Hydrogen has three isotopes namely hydrogen
Tritum (T), whereas opxygen exist in the form of five isotopes i.e.
('H), Ductirum enD) and
140, 0,
180. Due tothese isotopes water molecule canexist as H,0 with molecular 160,o
and
mass of 1k8 an
D,O with molecular mass of 22. There are some other forms HIDO, HTO
also.
d
The most common form is
H,0 (99.78%), D,0 exist only small amount (0.0222%) and
other forms exists in traces only.
D,O is called heavy water and it is
produced by enrichment from natural waters, It has
the importance because it is used in nuclear
technology as a moderate.
5.3 STRUCTURE, BONDING AND SHAPE OF H,O MOLECULE
In water, the central atom is oxygen is bonded to two hydrogen atoms. The clectronic
configuration of H-atom is ls' and that of oxygen atom in the ground state is Is2s 2p and
is represented in Fig. 5.1.

ls s 2p

000
)
Oxygenation in Ground State
Lone pair
ofelectrons

OO
V04.5°

Sp Hybridisation

Fig. 5.1. Tetrahedral (V-shaped) molecule of water formed by sp3

hybridisation.
In Figure 5.1, the dotted arrows represent electrons supplied by hydrogen atoms.
underlying 3-orbitals are not shown. Note-that the shape of the orbital containing a lone pan of
electrons is different from the shape of the orbital containing a bond pair of electrons.

Thus, there are two unpaired clectrons which can form two bonds with hydrogen atoi
without involving any xCitation Or the oxygen atom. But, in that case, the H,O molecule
WATER CHEMISTRY 235
involving only two orbitals, should have been linear and non polar like BcF,. This is not so
actually. Water molecule is known to have a bent structure and it is highly polar. This is
cxplained on the basis of hybridisation, The central oxygen atom in HaO molec ile has four
orbitals, the two containing lone pairs and thec other two containing bond pairs. These orbiials
undergo sp hybridisation to gnVe four sp" hybrid orbitals of equivalent energy. According
to Sidewick-Powell thcory, these hybridised orbitals give rise to a tetrahedral structure with
two corners occupied by hydregen atoms and tvo corners occupied by lone pairs of electrons.

(Fig. 5.1).
Since, the force of repulsion betwccn the two lone pairs of clectrons amongst themselves
is more than the force of repulsion betivecn a lonc pair and a bond pair which, in turn, is more

than the force of repulsion between two bond pairs of electrons. The two lone pairs will press
the two bonds pairs inward. Conscquently, the bond H-0-H in water will be reduced from
109.5° to 104.5°. The shape of vater molecule as also been explained in furthér chapter.

5.4 PHYSICAL PROPERTIES

Most of the unique properties of water are due to presence of H-bonding between its
molecules. Some of the important properties are discussed below:

1. Freezing and Boiling Point of Water

Water freezes at 0°C and boils at 100°C. In fact, water's freezing and boiling points
are the baseline with which temperature is measured. Water is unusual in that the solid form,
ice, is less dense than the liquid form, that is why ice floats on water. It is due to the property of
H-bonding in water that has been explained in next article.

2. Specificheat ofwater
Water has high specific heat value. This means that water can absorb a lot of heat
before it begins to get hot. That is why water is used in industries and in car radiator as a
coolant. The highest specific heat value of water also help in regulating the rate at which air
changes temperature. The temperature change in between seasons is gradual rather than
sudden, especially near the oceans because of high specific heat value of water.

3. Viscosity and surface tension

The substance which contain hydrogen bonding exist as associated molecules. So, their
flow becomes comparatively difficult. In other words,
they have higher viscosity and high surface
tension.

water has a very high surface tension. In other words, water is sticky and elastic, and
tends to clump together in drops rather than spread out in a thin film. Surface tension is responsible
TOr capillary action, which allows water (and its dissolved substances) to move through the
roots of plants and through the tiny blood vesscls in our bodies
 cONCEPTUAL ENGINEERING CHEMISTRY
236

4. Polar Characteristics
Due to its polar character, ionic salt dissolved in it and are ionised in it. Other polar
substances such as alcohols and acids also get dissolved in it. Water is a very good solvent, it is
rarely pure, and some of the properties of impure water can vary from those of the pure
substance. There are also many compounds which are insoluble in water, such as fats, oils and
other non-polar substances

5. Amphoteric Nature
Water is amphoteric, meaning that it is both an acid anda base-it produces H and
OH ions by self-ionization. This means the product of the concentrations ofH and OH is a
constant at a given temperature. the pH value of pure water is 7, which means it contains
equal number of H" ions and OH ions in it and is neutral in nature.
Based on the above mentinoed physical properties of water, the following conclusions
are important:
() The freezing point, boiling point, heat of fusion and heat of vaporization of water are
abnormally higher than those of the hydrides of the other elements of the same group
16 such as H,S, H,Se, H,Te, etc. This is due to the
presence of intermolecular hydrogen
bonding in H,O molecules which is, however, absent among the molecules of HS,
H,Se, H, Te, etc.
() Water has a higher specific hcat, thermal conductivity and surface tension than most
other liquids. These properties allow water to play a vital role in the biosphere. For
example, the high heat of vaporization and the high heat capacity of water are responsible
for moderation of the climate and body temperature of living organisms.

Gii) Water because of its high dielectricconstant(78.39)hasthe ability to ihssolve most of

the inorganic (ionic) compounds and is, therefore, regarded as a universal solvent.
Whereas solubility of ionic compounds takes place due to ion-dipole interafions (i.e.
salvation of ions), the solubility of covalcnt compounds such as alcohols, amines, urea,
glucose, sugar, cte. takes place due to the tendency of these molecules to form hydrogen
bonds with water.

(iv) Heavy water (D,0) has slightly higher values of physical constants because of its
higher molecular mass as compared to that of ordinary water (H,0).

5.5 HARDNESS OF WATER

Water which does not produce lather with soap solution readily, but forms a white
scum or precipitate is called hard water.
It is due to the presence of some dissolved salts in it. Soaps are sodium or potassium
salts of higher fatty acids like stearic acid, olcic acid and palmitic acid. When hard water is
treated with soap, it does not produce lather, rather soap gets precipitated in the form of insoluble
WATER CHEMISTRY 237

salts of calcium and magnesium. No lather iS formed until all these ions are completcly removed
gets wasted in the process.
and hence a large amount of soap

CaClh 2C,HCOONa 7H,cOo, Ca +2 NaCl

(Calcium chloride Sodium stearate Calcium stearate
from hard water) (Soap) (Insoluble ppt.)
Such precipitates are not formed with detergents, which are sulphonates of long chained
lather with soap is called soft Such does
alcohols. Water, which easily forms water. water
Ot contain calcium and magnestum salts in it. The process of emoving hardness from
water is called softening of
water

The main differences between the two types of water are summarized below

Hard Water Soft Water

Water which does not produce lather

1 Water which lathers easily on shaking|
with soap solution, is called "Soft
with soap solution readily, but forms a
white scum or precipitate is called Water"
"Hard Water".

Hard water contains dissolved salts 2. Soft water does not contain dissolved
2.
calcium and magnesium salts in it.
of calcium and magnesium in it.
3. In hard water, cleansing quality of soap 3. In soft water, cleansing quality of
is lowered and a lot of it is washed soap s not lowered and so soap is not
during washing and bathing. wasted during washing and bathing.

4. Due to the presence of dissolved hardness- 4. Less fuel and time are required for
producing salts, the boiling point of water cooking in soft water.
is elevated. Consequently, more fuel
and time are required for cooking.

5.5.1 Types of Hardness

Hardness of water is of two types
(A) Temporary hardness (B) Permanent hardness
(A) Temporary hardness (Carbonate Hardness or Alkaline Hardness):
i s caused due to the presence of bicarbonates of calcium and magnesium. If 1s
called temporary hardness because it can be removed easily by boiling8
The presence of bicarbonates in water is due to dissolution of insoluble carbonates n
the presence of
atmospheric CO,
A

238
cONCEPTUAL ENGINEERING CHEMISTON
CaCO +C0 +H,0 Ca(HC03)2 AISTRY
On boiling,
bicarbonates of calcium and magnesium get decomposed to give insoluhl
carbonates or hydroxides. These carbonates or hydroxides being insoluble ble
are
of precipitates and thus
temporary hardness is removed. removed in fo
orm
caHCO3 CaCO +H,O+ Co,T
MgHCO A Me(OH) +2C0,
Temporary hardness is also called carbonate hardness or
due to the presence of bicarbonates of alkaline hardness. t is
Ca and Mg, carbonates of
small extent and hydroxides of the Fe and other heavy metals
titration with standard acid solution hardness-producing metal ions. It can be determined byto
(say HCl) using methyl orange as an indicator.
(B) Permanent hardness
(non-carbonate or non-alkaline hardness)
It is due to the presence of chlorides and
is calledpermanent hardness, since it cannot be sulphates of calcium
removed by boiling.
and magnesium. It

However, it can be removed by using various

salts are not the chemical
agents. Calcium and magnesium
only salts responsible for hardness.
commonly present. However, all soluble salts of They mentioned because they are most
are
heavy metals cause hardness.
It is also called
non-carbonate or non-alkaline
subtracting the alkaline hardness from the total hardness. hardness. It can be determined by
Hard water has to softend
hard water not only consumes more
before it is used for domestic or industrial purpose, because
soap or detergent used for washing clothes but it shortens
the life of fabrics and clothes. Hard
water can damage the
Water is used in boilers for generating steam, but hard equipments used in industries.
water, if used, will form scales and
sludges in the pipelines which give rise many harmful effects. So, hard water must be converted
to soft water before using it for domestic
or industrial
purpose. Water has to be treated to
remove the unwanted
impurities present in it before using
it in different industries.
5.5.2 Disadvantages of Hard Water
Hard water contains large amounts of bicarbonates,
and magnesium dissolved in it. These dissolved salts cause
sulphates and chlorides of calcium
undesirable effects both in houses
and industries. Hard water causes number of
problems in domestic use, industrial use and in
boilers.These problems are explained below:
1. Problems in domestic use
Hard water causes many undesirable effects when used for domestic
purposes. Some
instances are given below:
(a) Wastage of Soap: A large amount of soap is wasted when hard water is used for
washing purposes. It is because hard water does not form lather with soap readily.
WATER CHEMISTRY 239
Most of the soap is wastcd in removing calcium and magnesium salts prescnt
soap forms lather with water
and only after this
nard watcr to form insoluble calcium and magnesium
(b) Spoiling clothes: Soap reactS witn
to the clothes the form of scum. These scums are not easy to
soap, which sticks in
move and make dirty marks on the clothes. The insoluble soaps also damage silk and

nylon fabrics.
Calcium and magnesium salts form incrustation inside the
(c) Deposition in kettles: an
kettles, ifhard water is boiled in it. It is duc to the formation of carbonates and hydroxides

boiling water. It wastes fuel. However, this incrustation can be removed by adding
a
in
little vinegar.
and other vegetable do not cook well in hard water.
d) Cooking: Pulses

2. Problems in industrial use

In paper industry, water is used along with soap for sizing the paper.
(a) Paper Industry:
salts present in it waste a good amount
If hard water is used, calcium and magnesium
of soap by forming insoluble precipitates.
used in textile industry for cleaning, washing and whitening
(b) Textile industry: Water is
hard water is used much soap is wasted.
of yarn. For such purposes, soap is required. If
for dyeing purposes, salts of calcium and magnesium
(c) Dyeing: If hard water is used
not give a homogeneous look.
spoil the desired shade and thus the dyed clothes do
are blocked due to precipitation of salts
(d) Choking and clogging problem: Water pipes
during boilingof hard water. This involves extra cost for maintenance and repair of
water pipes.

3. Problems in boilers
Huge quantity of water is used in boilers for generation of steam. If hard water is used
in the boiler, a number of difficulties arise which are listed as:

(a) Scale and sludge formation (b) Boiler Corrosion

(c) Priming and foaming (d) Caustic embrittlement

5.5.3 Softening of Hard

Water
There are many methods for the removal of hardness of water i.e. softening of hard
water. The most important and commonly used method is discussed below

Demineralization or Deionization or lon-Exchange Process

In this process, the ions prescnt in a solution are exchanged by ion-exchange resin. lon-
exchange resins are insoluble, cross-linked, high molecular weight organic polymers with a
porous structure and the functional groups attached to polymeric chains are responsible tor 1on-

Cxchange properties. They are of two types

 240
cONCEPTUAL ENGINEERING CHEMISTRY
)Cation exchange resins:
These are
styrene-divinylbenzene co-
CH-CH-CHh-ÇH-CH-CH
polymers. These resins have acidic functional
O
groups like -SO, H* or -CO0H which can So H
so H
exchange the cation by their hydrogen ions. Hence CH-CH-CH,
they are also called cation exchangers. The resins CH-CH CH-CH
with -S0, H" group are
stronger cation
exçhangers than those with COOH
functional
group. Following is the structure of a
typical cation $oH
exchange resin. Cation exchange resin
i) Anion exchange resins:
These are
styrene divinylbenzene or amine formaldehyde copolymers. they have amino
or
quaternary amnmonium or
quaternary
phosphonium ions as
integral
part of the
*****

-CH-CH-CHhÇH-CH-CH-CH- --.

resin matrix. These, after

treatment with
dil NaOH solution, become
capable to
exchange OH ions with anions HCNMe OH
AcMojOH
exchangers. Structure of anion exchange CH H CH
resins may be represented as --hC-CH CH-CH *

PROCESS
Column-I: The schematic layout O
of this process is shown in Fig. 5.2. H,CMe,OH H,CNMeOH
Anion exchange resin
The hard water is first passed
through column-I containing cation exchange resins, where all the cations
ions) in water
(Cat or Mg*
present get removed and equivalent amounts of H* ions are released
2 RH+Ca2+
R,Ca+2H
2 RH+Mg" R,Mg+2H*
Column-II: After this, the water is passed though column-II
exchange resins. containing anion

All the anions (HCOg,Clor S0 ions) present in water get removed and cquivalent
amounts of OH ions are released.

ROH+CI R'CI+OH
2ROH+SO R,SO, +20H
 WATER CHEMISTRY 241

Water + cO, ctc.

Water + Acid

Impure
water

C 0 , ctc.
(gases)

Cation ZAnion Steam

exchanger cxchanger
oo00000000000
Jacket
0000000000000o

00 GravCl ooo 80 Gravel ool

QOUUUUuvuvyO00 000000000000
bo00000õ000000|

Alkali for
P
regeneration
Acid for
Degasifier
regeneration Washings HWashings Demineralized
water
Fig.5.2. Demineralization byion exchangers.

H and OH ions, rcleased from cation and anion exchange resins columns, get combined
to give water deionized.

H +OH HO
The water is finally freed from dissolved gases like CO etc. by passing it through a
degasifier. It is a tower heated from sides by steam and it is connected to a vacuum pump. High
temperatureand low pressure reduces the quantity of dissolved gases.
The water coming out is free from all types of ions. Hence, it is called deionized or
demineralized water. It is also free from acidity or alkalinity. It is as pure as distilled water.

Regeneration:
When the cation and anion exchangers stop exchanging H" and OH ions, they are
known as exhausted resins, which can be regenerated as follows:
The exhausted cation exchanger is regenerated by passing a solution of dilute
HCl or
dilute HSO, through column-I.
The regeneration is represented as follows:

R,Ca+2H* 2RH +Ca2+

R,Mg +2H* 2RH+Mg*
The column is washed with deionized water and the washing is passed to a sink.
 242
cONCEPTUAL ENGINEERING HEMISTRY
The exhausted anion exchanger is regenerated by assing
through column-I1.
a solution of dilute
NaOH
The regeneration is represented
follows:
as

RCI+OHT ROH+CI +CI

R,SO +20OH 2ROH+S0
The column is washed with
deionized water
regenerated ion exchange resins can be reused for and the washing is passed to a sink, The
softening hard water again.

5.6 POLARITY AND HYDROGEN

BONDING
An important feature of
water is its
is that water is a polar nature. The effect of the electronic
polar molecule. Due to the difference structure
dipole moment pointing from each H to the in electronegativity,
there is a bond
O, making the
oxygen partially negative and each 6-
positive. Fig. 5.3 shows the partial hydrogen partially
in a water molecule. In charges on the atoms
on the
addition, lone pairs of electrons
the
oxygen atom are in the direction
hydrogen atoms. opposite
to the
Fig. 5.3. The partial charges on the
atoms in a water molecule
This results in a large molecular
dipole, pointing from a positive region between the two
hydrogen atoms to the
negative region of the oxygen atom. The charge differences cause
water molecules to be attracted to
each other, the
the relatively relatively positive areas being attracted to
negativeareas and to other polar molecules. This attraction
contributes to hydrogen
bonding, and explains many of the properties of water, such as
Water molecule contains highly
solvent action.
electronegative oxygen atom linked to hydrogen atom.
Thus, oxygen atom attracted the shared pair of electrons more and
this end of the molecules
become negative whereas the H-atom becomes
positive, The negative end of one molecule
attracts the positive end of other and
hydrogen bonding takes place as shown below:
&+
- -

0-
&+
-H.

HO+
HO+
Although hydrogen bonding is a relatively weak attraction compared to the covalent
bonds within the water molecule itself, it is responsible for a number of water's
physical
properties. These properties include its relatively high melting and boiling point temperatures:
more energy is required to break the hydrogen bonds between water molecules. In contrast,
hydrogen sulfide (H,S), has much weaker hydrogen bonding due to sulfur's lower
electronegativity. H2S is a gas at room temperature, in spite of hydrogen sulfide having nearly
WATER CHEMISTRY 243
twice the molar mass of water. 1he extra bonding between water molecules also gives liquid
water a largespecifíc heat capacity. 1his high heat capacity makes water a good heat storage
heat shield.
medium (coolant) and

Cohesion and adhesion

Water molecules stay close to each other (cohesion), due to the collective action of
hvdrogen bonds between water molecules. These hydrogen bonds are constantly breaking,
with new bonds being formed with different water molecules; but at any given time in a sample
of liquid water, a large portion of the molecules are held together by such bonds
Water also has high adhesion properties because of its polar nature. On smooth glass
surface, the water may form a thin Tilm because the molecular forces between glassand iwater

molecules (adhesive forces) are strongerthan the cohesive forces. biological cells and
In
with membrane and protein surfaces that are hydrophilic; that is,
organelles, water is in contact
surfaces that have a strong attraction for water. Irving Langmuir observed a strong repulsive
force between hydrophilic surtaces. To dehydrate hydrophilic surfaces-to remove the strongly
work against thse forces, called
held layers of water of hydration--requires doing substantial
hydration forces. These forces are very large but decrease rapidly over a nanometer or less.
They are important. in biology, particularly when cells are dehydrated by exposure to dry
atmospheres or to extracellular freezing.

5.7 EXPLAINATION OF LOWER DENSITY OFICE THAN WATER

In water, hydrogen bonds are formed between oxygen atom of one molecule and hydrogen
atoms of another molecule at definite angles.
Vacant Spaces
H4C
--O --
H,C H
-O
H
177 pm
95.7 pm

H
H-

H
-0
H
-0 - 0
- -0- - -
-O -
H-0, - -
H H
H
(a) (6)
Fig. 5.4. (a) Structure of water in the liquid form
(b) Tetrahedral arrangement of water molecules in ice.
 244 cONCEPTUAL ENGINEERING CHEMisTn
RY
In icc. water molecules are tctrahcdrally linked in which two hydrogen ato.
ns form
covalcnt bonds vith oxygen atom whilc the other two hydrogen atoms form hydrogen m
IFig, 5.4 (a)]. This results in the formation of open cage-luke structure as revealed hu bonds
Fig. 5.4(b)]. In ice, covalently bonded hydrogen are at lesser distancc (10A), whereas X-ray
two hydrogen bonds lic at a distance of 1.76A. It results in vacant
(10Å), whercas other
spaces in crystal structuure
and, therefore, gives rise to large volume for a
given mass of water. Therefore, density of iice
which is mass per unit volume is less than that of water
When ice melts, the open cage-like structure (Fig.
5.5) partially breaks, which brings
the water molccules closer by cntering into the vacant
spaces. As a result, volume
and density increases in the liquid state of water. That is decreases
why ice flots on water.
Note that is oxygen atom is linked to four
H-atoms, two by covalent bonds and two by
H-bond. Each water molccule is linked to four water
molecules tetrahedrally by H-bonds.
5.8 DENSITY OF WATER IS MAXIMUM AT 4C
As water is heated form 0°C i.e. 273 K (melting
of hydrogen bonds are broken and the molecules come point ice) onwards, more and more
of
more and more closer in the
As a result, the volume decreases and liquid state.
hence density increases. This
4°C i.c. 277 K, where water attains the process continues up to
maximum density. On heating further, the kinetic
energy of the molecules increases and the molecules move
4C, contraction effect predominates and above 4°C, the apart causing expansion. So up to
and overall expansion dominates over contraction
density decreases. So the value of density is maximum at 4°C.

H H
Vacant Vacant
space space O
H H
Vacant
space
H H

H
Fig.5.5. Open cage-like structure of ice.

5.9 THE AUTOIONIZATION OFWATER

Water undergoes self ionisation and forms ions per the
as
equation given below:
HO) + H,O() = H,0t + OH

The equilibrium constant, K, for the above reaction can be written as:
 246
WATER CHEMISTRY
KH0]loH].

1000
Since [H,O] = 8 55.56 M, and remains rather constant under any circumstance,

we usually write,

KH0j [OH] 10-14 (or I e-14)

=

pKw=-log Kw by definition)
= 14 (at 298 K)

For neutral water, [H30T=[OHJ 10

=
or l e at this temperature. Furthermore,
we define

pH=-loglH,0"]
pOH -loglOH]
pH pOH=7 at 298 K; (in neutral solutións)
words, pH+ oPH
=
14
In other

characters
5.9.1 Leveling effect of wåter and acid-base
The strength of strong acids and bases is decided by the self of water. In aqueous

solutions,the strongestacid and base are thehydronium ion, (H0t) and the hydroxide ion
and H,S04 completely ionize
(OH) respectively. Acids such as HCI, HNO3, HCIO3, HCIO4,
water. Furthermore,
in water, making them as strong as H,0* due to the leveling effect of
in their solutions.
strong acids, strong bases, and salts completely ionize aqueous
For example, HCl is a stronger acid than H,0, and the following reaction takes place
when HCl is dissotves in water.
HCI+H0 » C+H,0*
Similarly H,Sso, ionises in water in two steps, because it is a dibasic acid (Basicity = 2)

H,SO4 + H,0 HSO +H,0

HSO +H,0 S0+H,0*

On the other hand, a stong base also react with water to give the strong base species, OH
H,0+B OH+HB
HO + NHg OH + NH

5.9.2 Amphiprotic species

When an acid and a base differ by a proton, they are called a conjugate acid-base pair.
A water molecule is a weak acid and base, due to its ability to accept or donate a proton. Such
 CONCEPTUAL ENGINEERIN CHEMISTRY
246

properties make water an amphiprotic species. In fact, H,O", H,0 and OH are amphiprot
like some other conjugate acid-base pairs of weak acids and bases. protic,
Ifseveral acids and bases are dissolved in water, all cquilibria must beconsidered T"
estimate the pH of these solutions requires the exact treatment of several equilibrium constante
For example, many species dissolve in rain water, and many equilibria must be considered
Detail consideration and examples are given in Acid-Base Reactions.

HC1+H,0 C+H,0 )
H,C-COOH +H,0 H,C-CO0 +H,0* ..i)
Strong acids have a weak conjugate bases and vice versa.
For example, CF ion is weak conjugate base of the
strong acid HCl and H,C-CO00
ion is a strong conjugate base of the weak acetic acid
(CHCOOH).
HCI, being a strong acid ionizes completely and reaction (i) take place in the forward
direction. C ion being a week base cannot bring out the backward reaction.
Acetic acid (CH,COOH) being a weak acid does not ionise fully in the forward direction.
The acetate ion (H3C-COo) being
place in the backward direction.
astrong conjugate base favours the reaction (i) to take
Carbon dioxide in the air dissolve in rain water, lakes and
rivers, A solution of CO2
involves the following reaction:

HO) +CO,(g) H,CO,)

H,CO HCO +H*
HCO3 CO,4+H
HOH()+HOH() H,0* +OH

5.10 CHEMICAL PROPERTIES OF WATER

Water in Redox Reactions

Water displays a wide range of reactions. It behaves as an acid, a base, an oxiding
agent, a reducting agent and, as a ligand to metal ions. Some of these properties are discussed
below:
1. Stability.
Water is quite stable at ordinary temperature but deconmoscs into its elements a
ery
high temperature. The extent of decomposition is, however, very small. Even at 1500 K, it is
only 2%.

2H,0(g) 2H(g)+0,(8)
WATER CHEMISTRY
247
Water also decomposes into its clemonts; when olectricity is passed through it in
prescnce
small amount of an acid or an alkali,
of a

2H,O(0)Electriccuront
2H2(8)+ 02(8)
(At cathodo) (Al anoda)
2.Acid-base character

Water undergoes ionization to a small extent to give H30* (aq) and OH (aq) ions. As
has very low clectrical conductivity.
a result, pure water
H,00)+H,o)H,0'(aq)+OH"(aq)
Thus, water acts both as an acid and as a base and hence is sald to he amphoteric

in character.

For example, it can act as an acid towards NH2 and as a base towards H,S

Ho()+ NH, (aq) NHG (aq)+ OHr (aq)

Acid Base2 Acid Base
H,O0)+H,S(aq)>H,0* (aq) + HS (aq)
Base Acid2 Acid Base2
In general, water can act as a base towards acids stronger than itself and as an
acid towards bases stronger than it. It is amphoteric in nature. It úndergoes self ionization as
under:

H,o()+H;O() H,0*(ag) +OH" (aq)

Acid Base2 Acid2 Base

3. Redox reactions
Water also undergoes oxidation-reduction reactions.
(i) As an oxidising agent: Water reacts with number of active metals like Na, Ca, ctc.
liberating hydrogen gas.

H,O0)+2 20H"(aq)+H,(8): E -0.83V

2Na(s)+2H,0)
(Reductant)
(Oxidant)
2Na0H(aq) +H, (g)
Similarly, when steam is passed over red hot coke (1273 K), syngas is formed.
Syngas is mixture of CO and H2 in qual proportion, which is a good reducing agent.

C(s)+Ho(g).
(Reductant) Ni Co(g)+H2(8)
(Oxidant)
Syngas
In all these reactions, water acts as an oxidising agent and hence itself gets reduced
to hydrogen gas.
248
cONCEPTUAL ENGINEERING CHEMISTO
(ii) As a reducing agent: Water reacts with highly clectronogative clements like fuoe
liberating dioxygen and trioxygen rine

O2(8)+4H* (aq)+ 4c"-2H,0(); E +1.23V

2F,(s)+2H,o0)
Roductant)
(Oxidant)
0,(8)+4H*(ag) +4F" (aq)
or
3F,(8)+3H,O0)0,(8)+6F" (ag)+6H' (ag)
In there reactions, water acts as a
redhucing agent and hence Oreg gets
toeither 0, or O3. Similarly, oxidised
during photosynthesis in the presence of chlorophyl and
sunlight, it is oxidised to oxygen and carbohydrates such as cellulose is formcd.
Sunlight C,(H,0),+x02
xCO2+yH,0. Chlorophyll
4. Hydrolytic reactions
Water can hydrolyse many oxides
(metallic and non-metallic),
phosphides and other sålts. In these reactions, Ht and OH ions hydrides, carbides, nitrides,
of water interact with the
anions and cations of the compound
respectively leading to the formation of an acid or a base
both as shown below :
Ca0 (s) +H0 ()
Ca(OH)2 (aq) (a basc)
SO (g) + H,0 () HS0, (aq)
Sulphurous acid
PO10 (s) +6 H,O() 4 HPO4 (ag)
Phosphoric acid
CaH (s)+2H,O() Ca(OH), (aq) +2 H, g)
Calcium hydride

SiCL()+4H,O() Si(OH)4 +4 HCI (aq)

AICl (s)+ 6 H,O() [A1(H,0),13* (aq) + 3 Cr (aq)
CaC(s) + 2 H,O() Ca(OH )2 (aq)+ HC = CH(g) i.e. (C>H,)
Calcium carbide
Acetylene
Al4C3 (s) +12 H,00) 4
A1(OH), (aq)-+ 3 CH (g)
Aluminium carbide Methane
CaN2 (s)+ 6 H,O) 3 Ca(OH), (aq) +2 NH, (e)
Calcium nitride Ammonia
WATER CHEMISTRY

249
AIN (5)43 HO0) AOH), (aq) NH,(g) +
Aluminium nitride
Ammonia
CaP2s) +611,0) -> 3
Ca(OH), (aq) +2 PH,(g)
Calcium phosphide
Phosphine
Na,CO, (s) +
2H,00) 2 NaOH (aq) +
H,Co, (aq)
Since the hydrolysis of Na,CO, produces a
acid
strong base (NaOH) and a weak acid, i.e.,
carbonic (H2C03), thercfore, an aqueous solution of Na,CO, is alkaltne in nature.
In contrast, the hydrolysis of CuSO produces a weak base i.e.,
Cu(OH),
acid (H,SO4) thercforc, an aqueous solutton of CuSO, is acidic in nature.
and a strong

CuSO (s)+2 H,O0) Cu(OH)2 (aq)+ H,SO4 (aq)

5. Hydrate formation.
Many ionic compounds crystallise from water with one or more molecules of water
associatod with them. For cxample, BaCl,.2H,0, CuSO.5H,0, FeSO4.7H,0, Na,SO4.10H,0
tc. This water in combination with ionic salts is called water
of crystallisation and such
crystals are called hydrated salts. These hydrates can be classified into the.following three
categories
(i) Coordinated water: Water molecules are coordinated to the central metal ion to
form complex ions. For example, in nickel nitrate hexahydraie, ferric chloride
hexahydrate and chromium chloride bexahydrate, the six water molecules are linked to
the central ma Ni2*, Fe* or
Cr3 ion by coordinate bonds.
[Ni(OHP. (NO,)2, (Pe(H,0)513* 3Cr, [CI{H,0)%133 C
(ii) Hydrogen-bonded poet: Water molecules linked to some oxygen
are
anions by containing
hydrogen bonding. For example, in copper sulphate pentahydrate,
CuSO.5H,0, four H,0 molecules are linked to the central Cu2 by coordinate bonds
while the fifth H,O molecule is linked to the
sulphate (SO2-) ion by H-bonding. Thus,
CuSO4.5 H,0 may represented as
be
[CulH,0),15* SO.H,0.
(iii) Interstitial water:Water molecules are
present in interstitial sites or voids in the
crystal lattice. For example, in barium chloride dihydrate,
molecules occupy the voids in the crystal lattice. BaCl,.2H,0, the two H,0
5.11 WATERAS A SOLVENT
Water is an excellent solvent due to its high dielectric
constant. Substances dissolve in
water are known as hydrophilic
substances, while those that do not dissolved in water are
known as hydrophobic substances. The ability of a
substance to dissolve in water is determined
by whether or not the substance can form the strong attractive forces than water molecules
possesses with other water molecules i.c. hyerogen bonds. If a
substance can not overcome
ghese strong intermolecular forces, the molecules are precipitated out from the water.
 260
cONCEPTUAL ENGINEERING CHEMISTRY
When an ionic
polar compound is dissolved in water, it is surrounded
or

molecules (hydration). The rolatively small size of water moleculcs allows by iwater
by

solute. The partially negative dipole ends of the water aremolecl

to surround onc molecule of
many water
lcs
to positively charged componcnts of the solute, and vice
versa for the
attracto
acted
In gencral, ionic and polar substances such as
positive dipole ends
acids, alcohols, and salts
soluble in water, and non-polar substanccs such as
fats and oils
are relatively
arc not. Non-polar molecules
stay together in water because it is energctically more
favorable for the water
hydrogen bond to cach other than to cngage in van der molecules to
Waals interactions with non-polar
molecules.
An cxamplc of an ionic solute is
common salt, i.c. the sodium
into Nat cations and chloride, which separates
ClF anions, cach bcing surrounded by water molecules.
casily transported away from thcir crystalline lattice into The ions are then
solution.
An example of a non-iónic
solute is sugar (sucrose). The water
groups present in sugar which gets dissolved.dipoles
bonds with the polar -OH make hydrogen

SolvedSolved Typical Problems

Problem 1. Write the names of
isotopes of hydrogen. What is the
isotopes? mass ratio of these
Solution. Protium H, Deuterium H or D, Tritium H or T. The Mass ratio
deuterium: tritium= 1:2:3. of protium
Problem 2. Why does
hydrogen occur in a diatomic form rather than in a monatomic
form under normal conditions ? /
Solution. Hydrogen atom has only one electron and thus has one electron less than the
Inert gas configuration of helium. stable
Therefore, to achieve stable inert
electron of other hydrogen atom to configuration
it shares its single electron with gas of helium,
form a stable diatomic
molecule.
Problem 3. Among NH3, HO and HF, which would you expect to have highest
hydrogen bonding and why ? magnitude of
Solution. Due to greater eleetronegativity of N, 0, and F over, H, all these molecules
intermolecular H-bonding. undergo

H, H

--
WATER CHEMISTRY

However, since 261

clectroncgatiwty of F is the highest, therefore,
charg on hydrogcn, and -ve
chargo
on F is thec
highest and hence
magnitude of the +ve
the H-bonding 1s the strongcst in H-F clcctrostatic attraction or
Denhlem 4. What do you understand
by the term
its significance? 'auto-protolysis' of water ? What is

Solution. Auto-protolysis means self ionization of

water, It may be
representod as
H,O0+H00)
Acid Base2 H,o* (aq) +OH (a)
Acid2 Base
Due auto-protolysis, water is
to
base
amphoteric in nature, i.c., it reacts with both acids and
hases. It acts as a towards acids stronger than itself
and as an acid towards bases
than itsclf. For example, stronger

H,O(+ NH, (aq) NH (aq}+OH (aq)

Acid Base Acid2 Base

H,o(+H,S(aq)>H,o*
Base Acid2 Acid
(aq) +HSBase2(aq)
Problem 5. Consider the.reaction of water with F2 and
and reduction, which
suggest, in terms of ozidation
species are oxidised/reduced ?

Solution. 2F,(8)+2H,O() +
0,(g)+4H* (aq) +4F" (aq)
(Oxidant) (Reductant)

or
3F(g) +3H, O0)0,(g)+6H* (aq)+6F (aq)
(Oxidant) (Reductant)
In these reactions, water acts reducing agent and therefore, itself gets oxidised to
as a
either O, or Og while F2 acts as an oxidising agent and hence, itself reduced
to F ion.
Problem 6. What the temporary and permanent hardness of water ?
causes

Solution. Presence of bicarbonates of calcium and magnesium, i.c.

in water causes Ca(HCO) and Mg(HCO
temporary hardness and presence of soluble chlorides and sulphates of calcium
and magnesium, i.e., CaCl2, CaSO4,
MgCl2 and MgSO4 in water causes permaneat hardness.
Problem 7. Is demineralised or distilled water useful fot
how can it be made useful?
drinking purposes ? If not,
Solution. Demineralised or distilled water is not useful for drinking purposes, since it does not
contain even useful minerals. Therefore, to make it useful for drinking purposes, useful minerals
inproper amounts should be added to demineralised.or distilled water.
Problem 8. Describe the usefulness of water in biosphere and biological systems.
Solution. Water is essential for all forms of life. It constitutes about 65-70% of
the Douy
wCight of animals and.plants. In comparison to other liquids, water has a high specific heat,
 262 cONCEPTUAL ENGINEERIN CHEMISTRY

thermal conductivity, surface tension, dipolc moment and diclectric constant et

tc. These
properties allow water to play a key role in biosphere. The high heat of vaporisation and
and heat
capacity are responsiblec for moderation of the climate and
body temperature of living beings
is an excellent solvent for transportation
of and other nutrients for
minerals cings. It
plant and:animal
metabolism. Water is also required for photosynthesis in plants which releases 0, into
atmosphere. the
Problem 9. Write chemical reactions to show the
amphoteric nature of water.
Solution. Water is amphoteric in character, i.e., it behaves both as an acid
as well as
With acids (e.g. HS stronger than itsclf, it behaves as a a base
base and with bases (e. g. NH,)
stronger than itself, it acts as an acid. ,

H,O0+HS(aq)
Base
H,0* (aq) +HS (aq)
Acid Acid Base2
H,O(+ NH, (aq) NH; (aq+OH (aq)
Acid Base2 Acid2 Base
Problem 10. What properties of water make it
useful as a solvent ? What type of
compounds can it (i) dissolve (ii) hydrolyse ?
Solution. (i) Water has a high dielectric constant
Because of these properties, water dissolves (79.39) and high dipole moment (1.84 D).
most of the
many covalent inorganic (ionic) compounds and
compounds. That is why water, is called a universal solvent.
Whereas ionic compounds dissolve in water due to
ions, covalent compounds such as alcohols, amines, urea, ion-dipole interaction or salvation of
due to H-bonding. glucose, sugar, etc. dissolve in water
(ii) Water can hydrolyse many oxides (metallic or
non-metallic),
phosphides and other salts. In these reactions, H" and OH- ions ofhydrides, carbides, nitrides,
water interact with anions
and cations respectively leading to the formation of an
acid or a ba[e or both as shown below:
Ca0 (s)+H,0 ()
Ca(OH)2 (aq)
SO (g)+Ha0 ()>H,S0, (ag)
CaH, (s)+2H,00) Ca(OH), (aq) +2 H (g)
CaC2 ()+2H,0 ( Ca(OH)> (aq)+ HC=CH(g)
Acetylene
Problem 12. What is the difference between the terms
'hydrolysis' and 'hydration' ?
Solution. Interaction of H* and OH- ions of
H,0 with the anion and the cation of a salt
respectively to give the original acid and the original base is called hydrolysis. For example,
Na,CO +2H,0 2 2 NaOH + N,CO3
Salt Base Acid
 253
WATER CHEMISTRY

On the other hand, hydration mcans addition of H,O to ions or molecules to form
ions hydrated
or salts. For cxamplc,
hydrated
Na'Cl (s) +H,0 () Na (aq)+ C (aq)
Salt
CuSO (s) + 5 H,0 () CuSO.5 H,0 (s)

(Colourless) (Blue)
13. Knowing the properties of H,0 and D,0, do you think that D,0 can be
Problem 13.
drinking purposes ?
used for
an Hcavy water is injurious to human beings, plants and animals since it slows down the

rates of reactions occurring in them. Thus, heavy water does not support life so well as does
ordinary water.

nahlem 14. Which isotope of hydrogen (1)

does not contain neutrons, (ii) contains
and neutrons, (iii) is radioactive.
eaual number of protons
Solution. () Protium (11) Deuterium (ii) Tritium.
+ 1, (ii) -1 and
Problem 15. Name one compound each in which hydrogen exists (i)
oxidation state.
(ii) zero
Solution. () HO or H,0 or NH3 (ü) NaH or CaH (i) H2
Problem 16. What is the importance of heavy water with regard to nuelearpower
generation ?
moderator to slow down the neutrons produced as a result of fission
Solution. It is used as a

and thus helps to control the nuclear reactions.

Problem 17. Why is sodium chloride less soluble in heavy water than in ordinary water?
Solution. Due to lower dielectric constant of D,0 over H,0, NaCl is less soluble in D,0 than
in H,0.
Problem 18. Explain why electrolysis of ordinary water occurs faster than heavy water?
Solution. Due to lower bond dissociation energy of protium bonds in H-0-H than deuterium
bonds in D-0-D, electrolysis of H,0 occurs much faster than that of D,O.
Problem 19. The boiling point of H,O is higher than that of H,S. Explain.
Solution. Due to extensive intermolecular H-bonding in H,0, the b.p. of H,0 is much higher
than that of H,S.
Problem 20. What do you mean by hard and soft water.
Solution. The water which does not produce lather with soap solution, but forms a white
precipitate is called hard water. it contains dissolved calcium and magnesium salts which torm
scum with soap solution.

Soft water gives lather with soap solution not contain dissolved salts
readily. It does
and so it forms lather rather than scum or precipitate with soap solution.